@article {2413,
	title = {Spectroscopic and electronic structure studies of the mu(4)-sulfide bridged tetranuclear Cu(Z) cluster in N(2)O reductase: molecular insight into the catalytic mechanism},
	journal = {J Am Chem Soc},
	volume = {124},
	number = {35},
	year = {2002},
	note = {<p>0002-7863 (Print)0002-7863 (Linking)Journal ArticleResearch Support, Non-U.S. Gov{\textquoteright}tResearch Support, U.S. Gov{\textquoteright}t, P.H.S.</p>
},
	month = {Sep 4},
	pages = {10497-507},
	abstract = {<p>Spectroscopic methods combined with density functional calculations are used to develop a detailed bonding description of the mu(4)-sulfide bridged tetranuclear Cu(Z) cluster in N(2)O reductase. The ground state of Cu(Z) has the 1Cu(II)/3Cu(I) configuration. The single electron hole dominantly resides on one Cu atom (Cu(I)) and partially delocalizes onto a second Cu atom (Cu(II)) via a Cu(I)-S-Cu(II) sigma/sigma superexchange pathway which is manifested by a Cu(II) --\&gt; Cu(I) intervalence transfer transition in absorption. The observed excited-state spectral features of Cu(Z) are dominated by the S --\&gt; Cu(I) charge-transfer transitions and Cu(I) based d-d transitions. The intensity pattern of individual S --\&gt; Cu(I) charge-transfer transitions reflects different bonding interactions of the sulfur valence orbitals with the four Cu{\textquoteright}s in the Cu(Z) cluster, which are consistent with the individual Cu-S force constants obtained from a normal coordinate analysis of the Cu(Z) resonance Raman frequencies and profiles. The Cu(I) d orbital splitting pattern correlates with its distorted T-shaped ligand field geometry and accounts for the observed low g( parallel ) value of Cu(Z) in EPR. The dominantly localized electronic structure description of the Cu(Z) site results from interactions of Cu(II) with the two additional Cu{\textquoteright}s of the cluster (Cu(III)/Cu(IV)), where the Cu-Cu electrostatic interactions lead to hole localization with no metal-metal bonding. The substrate binding edge of Cu(Z) has a dominantly oxidized Cu(I) and a dominantly reduced Cu(IV). The electronic structure description of Cu(Z) provides a strategy to overcome the reaction barrier of N(2)O reduction at this Cu(I)/Cu(IV) edge by simultaneous two-electron transfer to N(2)O in a bridged binding mode. One electron can be donated directly from Cu(IV) and the other from Cu(II) through the Cu(II)-S-Cu(I) sigma/sigma superexchange pathway. A frontier orbital scheme provides molecular insight into the catalytic mechanism of N(2)O reduction by the Cu(Z) cluster.</p>
},
	keywords = {Catalysis, Circular Dichroism, Copper/*chemistry, Crystallography, X-Ray, Electron Spin Resonance Spectroscopy, Histidine/chemistry, Models, Molecular, Oxidoreductases/*chemistry/*metabolism, Spectrum Analysis, Raman/methods, Sulfides/chemistry, Thermodynamics},
	url = {http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve\&db=PubMed\&dopt=Citation\&list_uids=12197752 },
	author = {Chen, P. and Cabrito, I. and Moura, J. J. and Moura, I. and Solomon, E. I.}
}
